Biomass-derived materials for electrochemical energy storages

Accepted Manuscript Title: Biomass-derived materials for electrochemical energy storages Author: Lixue Zhang Zhihong Liu Guanglei Cui Liquan Chen PII: DOI: Reference:

S0079-6700(14)00105-1 http://dx.doi.org/doi:10.1016/j.progpolymsci.2014.09.003 JPPS 893

To appear in:

Progress in Polymer Science

Received date: Revised date: Accepted date:

11-4-2014 28-8-2014 22-9-2014

Please cite this article as: Zhang L, Liu Z, Cui G, Chen L, Biomass-derived materials for electrochemical energy storages, Progress in Polymer Science (2014), http://dx.doi.org/10.1016/j.progpolymsci.2014.09.003 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Biomass-derived materials for electrochemical energy storages Lixue Zhang1, Zhihong Liu1, Guanglei Cui1, *, and Liquan Chen1, 2 1

Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of

Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao

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266101, China Key Laboratory for Renewable Energy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

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Tel: +86-532-80662746, Fax: +86-532-80662744

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*Corresponding author: E-mail: [email protected],

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Abstract: During the past decade humans have witnessed dramatic expansion of fundamental research as well as the commercialization in the area of electrochemical energy storage, which is driven by the urgent demand by portable electronic devices, electric

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vehicles, transportation and storage of renewable energy for the power grid in the clean energy economy. Li-secondary batteries and electrochemical capacitors can

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efficiently convert stored chemical energy into electrical energy, and are currently the

rapid-growing rechargeable devices. However, the characteristic (including energy

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density, cost, and safety issues, etc.) reported for these current rechargeable devices still cannot meet the requirements for electric vehicles and grid energy storage, which

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are mainly caused by the limited properties of the key materials (e.g. anode, cathode, electrolyte, separator, and binder) employed by these devices. Moreover, these key materials are normally far from renewable and sustainable. Therefore great challenges

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and opportunities remain to be realized are to search green and low-cost materials with high performances. A large number of the properties of biomass materials-such

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as renewable, low-cost, earth-abundant, specific structures, mechanical property and

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many others-are very attractive. These properties endow that biomass could replace some key materials in electrochemical energy storage systems. In this review, we

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focus on the fundamentals and applications of biomass-derived materials in electrochemical energy storage techniques. Specifically, we summarize the recent advances of the utilization of various biomasses as separators, binders and electrode materials. Finally, several perspectives related to the biomass-derived materials for electrochemical energy storages are proposed based on the reported progress and our own evaluation, aiming to provides some possible research directions in this field.

Keywords: Biomass-derived materials; electrochemical energy storages; separators; binders; electrode materials.

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Table of Contents 1. Introduction 2. Overview of biomass materials

3.1 Cellulose materials for alkaline battery separators

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3. Biomass-derived battery separators

3.2 Cellulose materials for electrochemical capacitor separators

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3.3 Commercial paper-derived lithium ion battery separators

3.4 Micro-/nano-fibrillated cellulose-derived lithium ion battery separators

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3.5 Cellulose composite-derived lithium ion battery separators

4. Biomass-derived green binders

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3.6 Bio-inspired materials for battery separators

4.2 Alginate-derived binder

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4.1 Carboxymethyl cellulose -derived binder

4.3 β-Cyclodextrin -derived binder

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4.4 Amylopectin-derived binder

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4.5 Gelatin-derived binder

5. Biomass-derived electrodes

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5.1 Conducting polymer/biomass composites as electrode materials 5.2 Carbon nanomaterials/biomass composites as electrode materials 5.3 Biomass-derived small molecules as electrode materials

6. Conclusion and perspectives 7. Acknowledgements 8. References

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1. Introduction In the 21st century, with the rapid demand of electric vehicles and portable electric devices, a new energy economy is emerging, which is critically based on the cheap

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and sustainable energy supply. Undoubtedly, to exploit clean, sustainable and secure energy supplies is one of the most important scientific and technical challenges for

humans [1-3]. State-of-the-art electrochemical energy storage devices, typically

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including Li-ion batteries (LIBs) and electrochemical capacitors [4-7], provide a

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potential and promising solution since they can efficiently store energy from sustainable sources such as the wind and solar power and then work as power sources. These energy storage devices are typically composed of a negative electrode (anode),

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a positive electrode (cathode), an electrolyte that allows ions transport, a separator that separates the two electrodes, and current collectors that allow current to flow out

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of the cell to perform work. The overall performance of these energy devices depends intimately on the properties of the materials used. Hence, material science and

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technology hold the key to new generations of energy storage devices. Numerous

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materials, including various anodes, cathodes, separators, binders, and electrolytes, are designed and fabricated to improve the performances of LIBs and electrochemical

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capacitors [4-10].

The principal remaining challenges for the future development and widespread of

energy storage, other than performance and safety enhancements, are the reduction of both production and overall device costs, the realization of flexible devices, the identification of environmentally friendly materials and production processes and the development of easily recyclable and up-scalable systems [1-3]. Presently, these electrochemical energy devices mainly depend on the substantive use of components that are far from renewable and sustainable, for instance, inorganic compounds that often require rare metals as electrode materials, expensive polymers as separators and binders, and organic solutions as electrolytes, and so forth [4-7]. Broad applications of electrochemical energy devices require more abundant and inexpensive materials than those currently available. As Armand and Tarascon wrote in 2008, “Researchers must find a sustainable way of providing the power our modern lifestyles demand” [1], a 4

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consensus forms across the world that it is highly urgent and desired to decrease the consumption of non-sustainable electrochemical energy device resources by developing materials from easily accessible and renewable sources. Among numerous candidates, biomass-derived materials have gained increasing attention as attractive components of various electrochemical energy devices.

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Biomass is biological material derived from living, or recently living organisms. As earth-abundant renewable energy source, biomass is typically used directly via

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combustion to produce heat, or used indirectly after converting it to various forms of

biofuel [11-12]. However, the more intriguing and promising utilization of biomass in

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energy storage is to replace non-sustainable components in electrochemical energy devices, such as separators, binders, and electroactive electrode materials [13-15]. In

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the recent years, many significant efforts have been put into developing sustainable and high-performance biomass and/or biomass-derived materials for energy storage,

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and several significant review articles related to these research fields have been presented. Nyholm et al. reported the progress toward flexible polymer and paperbased energy storage devices [13]. Cui et al. reviewed the state-of-the-art flexible

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energy and electronic devices based on nanostructured papers [14]. Jabbour et al.

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summarized the progress of cellulose-based LIBs [15]. However, there is no a

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systemic review related to the applications of diverse biomasses and their polymer derivatives in electrochemical energy storages yet. In this review, we will give a short introduction of biomass materials, and then focus on recent progresses of biomassderived materials as advanced separators, binders, and electrode materials in electrochemical energy storages, and finally provide an overview and outlook about these fascinating research fields. 2. Overview of biomass material Biomass is all biologically-produced matter based on carbon, hydrogen and oxygen. The estimated biomass production in the world is 146 billion tons a year, consisting of mostly wild plant growth [16]. Biomass most often refers to plants or plant-derived materials, specifically called lignocellulosic biomass. In addition to lignocellulosic biomass, marine organisms also constitute a large part of biomass materials. It is well known that biomass has been widely applied in many fields, and 5

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the application of a particular type of biomass depends on the chemical and physical properties of the macromolecules [17]. In this review, several biomass-derivatives materials that have been widely used for energy storage devices, including cellulose, alginate, and some others, are mainly mentioned. The basic information of cellulose and alginate, including manufacture methods, molecular structures and properties, is

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summarized in Table 1. ------Table 1------

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As the most important skeletal component in plants, the polysaccharide cellulose is an almost inexhaustible polymeric raw material with fascinating structure and

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properties. Formed by the repeated connection of D-glucose building blocks, the highly functionalized, linear stiff-chain homopolymers is characterized by its

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hydrophilicity, biodegradability, broad chemical modifying capacity, and its formation of versatile semicrystalline fiber morphologies [18]. The nature of cellulose fibers is

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affected by the source of the raw material stock, e.g. wood pulp versus cotton linters, and the chemistry and mechanics of the fibers forming process. Interestingly, cellulose exists in hierarchical structure from micrometric cellulose fibers to nanocelluloses and

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water/solvent soluble cellulose derivatives, which promises an expected porosity (Fig.

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1) [19]. For instance, thousands of microfibrils cellulose assembles one tracheid in

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wood fiber, which has a multichannel, mesoporous structure and allows for the intercellular transportation of water and mineral salts (Fig. 1) [19]. Over the last 10 years, celluloses, especially nanocellulose, have attracted an ever increasing attention for the production of cellulose based nanocomposite materials, due to their high strength and stiffness combined with low weight, biodegradability and renewability [20].

------Fig. 1------

Marine polysaccharides, including alginate, chitin, agar and carrageenan, can be easily obtained from diverse marine organisms such as fishery products, seaweeds, microalgae, microorganisms, and corals [21]. Since these organisms inhabit in a very diverse marine environments, marine polysaccharides exhibit some unique properties, which are useful in a variety of applications such as food technology, biotechnology, pharmacy, and chemical industries. For instance, alginate is a naturally occurring 6

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anionic polymer typically obtained from brown seaweed, and typically alginate is a linear copolymer with homopolymeric blocks of (1-4)-linked β-D-mannuronate and its C-5 epimer α-L-guluronate residues. Due to its biocompatibility, low toxicity, relatively low cost, and mild gelation by addition of cations, alginate is widely used in food industry and pharmaceutical industry.

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3. Biomass-derived separators

Battery separator, a porous membrane placed between electrodes of opposite

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polarity, serves to prevent contact between the positive electrode and the negative

electrode and also plays a very important role in improving battery performance and

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enhancing its safety [22-23]. In the present battery production, the separator is impregnated typically into a mixture of supporting electrolyte (e.g. LiPF6 salts) and

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organic solvents such as ethylene carbonate (EC), ethyl methyl carbonate, and diethyl carbonate. A number of factors must be considered in selecting the suitable separator

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for a practical battery, and the general characteristic and requirements of separators are well illustrated in the review by Aoroa and Zhang (as shown in Table 2) [24]. Actually the data summarized in Table 2 are mainly focus on the polyolefin

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separators, and these parameters of nonwoven separators are somewhat depend on

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their specific materials and configurations.

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------Table 2------

Many researchers are interested in high-power LIBs due to their excellent

properties, resulting in the expansion in the use of large-scale LIBs in the power market and power grid areas. These emerging markets have led to new demands on separators for LIBs [22, 23, 25]. The most widely used separators in LIBs are fabricated from polyolefins, predominantly polyethylene (PE), polypropylene (PP) and their copolymers. These polyolefin separators have many advantageous attributes in terms of practical application to commercialized LIBs, such as low cost, proper mechanical strength and pore structure, electrochemical stability, and thermal shutdown properties [22, 26]. However, these separators suffered from a severe challenge in large shrinkage ratio at relatively high temperature of more than 100 °C. Moreover, their intrinsically hydrophobic character and low porosity raise serious concerns over insufficient electrolyte wettability, which could directly impair ionic 7

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transport through the separators and deteriorate cycle lives. Recently many approaches have been proposed to improve this insufficient heat resistance of microporous polyolefin separators including the ceramic coating on the surface of microporous membrane [27] and surface grafting modification using plasma treatments or electron beam irradiation [28, 29]. The most used fillers incorporated

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into the polymer hosts are inert oxide ceramics (Al2O3, SiO2, TiO2) and molecular

sieves (zeolites) with the main function of increasing wettability, mechanical stability

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and thermal dimensional stability of the separators [30, 31]. Despite these advances, it

is difficult to fully ensure electrical isolation between electrodes due to their

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inessential poor thermal shrinkage and weak transverse mechanical properties for intrinsic polyolefin materials at elevated temperature [32, 33]. In addition, the high

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processing cost and exhaustible fossil derived materials of polyolefin separators remains a critical burden on manufacture boosting and environments. Hence, a more

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advanced separator that can overcome these stringent shortcomings of polyolefin separators is urgently needed for facilitating the successful development of highenergy density/high-power density cells.

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Luckily, sustainable biomass-derived separators including cellulose, chitin and

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alginate, that exhibit superior wettability and thermal stability, are demonstrated as

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promising alternatives to conventional polyolefin separators for state-of-the-art electrochemical energy storage devices. These hydrophilic stiff-chain homopolymers endowed super solvophilicity, wettability, recycling, accessible to electrolyte and better thermal stability (over 230 °C) than polyolefin. Actually, cellulose and cellulose composite separators were initially explored for using in alkaline batteries. In recent 30 years, cellulose nonwoven has been widely explored as separators for LIBs and electrochemical capacitors. The common properties of biomass-based separators for alkaline batteries, electrochemical capacitors and LIBs include: (1) favorable separator surface and interface wettability by electrolyte, (2) high ion conductivity, and (3) large-scale production with low cost. 3.1 Cellulose materials for alkaline battery separators About 70 years ago, the utility of regenerated cellulose membrane as a battery separator was recognized as a forward step which advanced the silver/zinc battery to a 8

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practical system. In 1941, Henri Andre, a pioneer of regenerated cellulose membrane, discovered that the short life of the silver/zinc battery system could be considerably improved by the introduction of a suitable cellulose semipermeable separator [34]. Then, for their excellent wettability, low processing cost, high porosity, good mechanical properties and light weight, paper sheets prepared using alkaline-resistant

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cellulose pulp or other cellulosic components were successfully used in a series of

commercially available alkaline batteries including alkaline manganese cell,

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nickel/cadmium industrial batteries, zinc/air cells, silver/cadmium batteries, as well as in silver/zinc batteries [35]. Although the electrolytes are different from one to

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another, the similar fundamental properties and problems for separator films are commonly observed in these systems. Harlan Lewis studied the properties of

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cellulosic separator and their relationships with the cycle- and wet-life information from model electrochemical cells as a functional of separator composition on an

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alkaline chemistry rechargeable cell set [36].

Alkaline battery accounts for 80% of manufactured batteries in the US and over 10 billion individual units produced worldwide, and the cellulose based separators for

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alkaline battery are still one of the intensive research focuses. Recently, some new

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progress related to cellulose materials for alkaline battery separator was achieved.

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Wang et al. fabricated alkaline Zn/MnO2 separator with an ultra-fine fibrillated Lyocell fibers by wet-laid nonwoven method, and the resulting separators manifested better properties than commercial separator especially in thickness and pore size [37]. Similarly, Toshimitsu Harada disclosed an alkaline battery composite separator including alkali-resistance synthetic fiber, fibrillated organic solvent-spun cellulose fiber and mercerized pulp, wherein the cellulose fiber intertwines with the mercerized pulp. This kind of composite separator exhibited excellent properties in denseness, electrolyte retention capability, and alkali resistance and great stiffness strength [38]. Most recently, Nippon Kodoshi Corporation developed an alkaline battery separator on the basis of cellulose. This separator is constructed by including 20-90 mass% cellulose fiber and having the remains being an alkali-resistant synthetic fiber, and can suppress reduction in the characteristics of the alkaline battery after storage [39]. 3.2 Cellulose materials for electrochemical capacitor separators 9

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Electrochemical capacitors store the energy at the electrode/electrolyte interface of high surface area materials, such as porous carbons or some metal oxides. Although their energy densities are somewhat low, electrochemical capacitors possess of many important benefits, such as high power density, long lifetime, low cost, good cycle performance and rate capability, etc. Electrochemical capacitors have been

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commercially available for more 30 years, and have been widely applied in consumer electronic products, (alternative) power source, and electric vehicles, etc. [7, 40].

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In principle, electrochemical capacitor can work without a separator if a suitable distance between electrodes can be kept. However, practically, separators are

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necessary for the electrochemical capacitors to prevent from short circuits. Owing to the large market, the separator of electrochemical capacitors should be quite low in

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price and quite high in quality. Numerous studies have been demonstrated that cellulose-derived separators are very suitable for electrochemical capacitors

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applications, due to their low cost and high porosity (in the order of 45–90%) [7]. Currently, numerous cellulose based paper products are available for use as separator membranes in commercially available electrochemical capacitor systems. Such

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products include single-sheet cellulose fiber materials, multi-sheet cellulosic and

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composite materials with various densities which ostensibly yield the desirable

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properties, i.e., electrolyte absorption, electronic insulation, and physical strength [41]. Although such separator papers perform quite well in the intended physical compression type of electrochemical capacitors, the resistance between these papers and the desirable cell electrode compositions (particularly in preferred thermal laminating procedures), restricts use of these papers in the fabrication of unitary laminated cell structures [42]. In additions, paper separators often suffer from performance deterioration at high voltage and water contamination in electrochemical capacitors, thus it is critical to overcome these obstacles for the development of paper separator-based capacitors. 3.3 Commercial paper-derived LIB separators Some cellulose papers, which are manufactured using commercial cellulose papers, as advanced separators of lithium-based batteries have been reported. In 1996, Kuribayashi carried out a systematic investigation on the use of thin hybrid cellulose 10

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separators for LIBs. These paper separators, comprising fibrilliform cellulosic fibers embedded in a microporous cellulosic matrix soaked with an aprotic solvent, were supplied by Nippon Kodoshi Corporation and Tomiyama Pure Chemical Industry. The proposed separators showed fair-to-moderate physical strength, an apparent completely freedom from pinholes, and a comparable impedance to that of

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conventional polyolefin separators [43]. The commercial rice paper, a low cost and

highly porous, flexible cellulose membrane, invented over a thousand years ago in

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China for traditional Chinese painting and calligraphy, was recently explored for the

application as separator of LIBs, which exhibit fair cycling electrochemical stability at

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low current density [44].

The cellulosic papers directly as separators suffer from moisture absorption owing

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to the hygroscopic nature. The moisture content of cellulose fibers can range between 2-12×104 ppm [45], which severely exceeds the humidity requirement of a LIB

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electrolyte (not exceed ca. 20-50 ppm). A high humidity condition usually leads to the degradation of lithium salts, particularly LiPF6 hydrolysis and HF formation [46]. Nevertheless, as demonstrated in recent works, this apparent limitation of moisture

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accessibility can be solved by prolonged thermal treatment over 120 °C owing to its

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on cellulose [47].

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superior thermal stability of cellulose which allows removing most of water adsorbed

Due to the high thermal stability and cost-effective of cellulose materials, the

commercial cellulose papers can be used as separators for LIBs. However, the macro/microfiber-based cellulose papers face some stringent limitations in securing a satisfactory porous configuration (particularly, pore size and pore size distribution, and thermal shutdown effect), and mechanical strength and flammable characteristic, which in turn hamper their application for LIB separators. As a result, it seems not very suitable to directly use commercial papers as LIB separators. 3.4 Micro-/nano-fibrillated cellulose-derived LIB separators Micro-/nano-fibrillated elluloses, consisted of highly crystalline domains and

attractive nanoporous structure, possess excellent mechanical property and attractive porous structure. These fascinating characteristics would endow micro-/nanocellulose membrane as a very promising separator for LIBs. In the most recent years, 11

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Lee and his colleagues devoted much contribution in the field of nanocellulose-based separators. They developed eco-friendly cellulose nanofibers (CNFs) paper-derived separators with a salient feature of electrolyte-philic, nanoscale labyrinth structure established between closely piled nanocelluloses. The unusual porous structure is fine-tuned by varying the composition ratio of the solvent mixture (isopropyl alcohol

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(IPA)/water) in the CNFs suspension, wherein IPA is introduced as a CNFsdisassembling agent while water promotes dense packing of CNFs. For example,

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when the IPA content is 95%, the CNFs separator provides a porous structure containing many nanopores formed between highly interconnected CNFs (Fig. 2A).

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Compared with the PP/PE/PP separator, the CNFs separator presents a much improved wettability of liquid electrolyte (Fig. 2B). Due to the nanoporous structure

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and strong affinity for liquid electrolyte, these CNFs paper-derivated separator shows good cycling performance (Fig. 2C) and rate capability [48].

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------Fig. 2------

However, CNFs paper separators suffer from a limitation in providing highlyporous structure, which may stagger ionic transport via the liquid electrolyte-filled

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CNFs paper separator. This structural shortcoming may arise from the dense packing

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of CNFs for the strong hydrogen bonding between nanocellulose [49-51]. Lee et al.

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recently designed a colloidal SiO2 nanoparticle-based strategy to tune the porous structure of CNFs paper separators, in which the SiO2 nanoparticles are introduced as a CNFs-disassembling agent instead of IPA. The SiO2 nanoparticles are dispersed

between the CNFs and allow loose packing of CNFs, thereby facilitating the formation of a more developed porous structure (Fig. 2D). With increasing the content of hydrophilic SiO2 nanoparticles, the as-prepared SiO2-CNFs exhibit the greater and

greater electrolyte immersion-height than the PP/PE/PP separator (Fig. 2E). With well-developed porous structure and optimized membrane properties, the SiO2-CNFs

paper separator greatly improves the cycle performance and rate capability (Fig. 2F) [52]. Although the above developed CNFs paper-derived separators exhibited an enhanced cell performance, these separators still suffered from a poor mechanical strength and the fabrication process is somewhat complicated. It still remains a 12

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challenge to produce nanocellulose separator in a large-scale, low-cost and environmental friendly approach. To simplify the fabrication of CNFs-based separator, Lee et al. also developed a new method, which relies on simply mixing cellulose nanofibrils and a pore-forming resin. The pore-forming resin, consisting of polyethylene glycol, polypropylene alcohol, PP, and hydroxyl cellulose, was explored

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to form micropores [53]. 3.5 Cellulose composite-derived LIB separators

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In recent years, many efforts have been made to improve the porous structure,

mechanical property and electrochemical performance of the cellulose based

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separators for LIBs. Among them, incorporating other polymer materials with the cellulose nonwoven to form composite separators seems a very promising approach. It

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can improve the mechanical property of cellulose separator, and at the same time, it might bring a synergetic effect for the composite separator. The principal features of

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battery separators based on cellulose derived composite materials are summarized in Table 3.

------Table. 3------

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In order to improve the separator performance with minimal water adsorption and

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enlarged voltage window for high energy battery, Cui et al., from Chinese Academy of

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Sciences, explored a cellulose-based composite nonwoven via an electrospinning technique for LIB separator. The nonwoven mat of cellulose was prepared by deacetylation, and then formed composite with poly(vinylidene fluoride-cohexafluoropropylene) (PVDF-HFP) by dip coating, and followed by calendaring. Compared with cellulose nonwoven, the cellulose/PVDF-HFP composite nonwoven shows smaller pore sizes and uniform pore distribution (Fig. 3A, B), which might be in favor of mitigating self-discharge and achieving uniform current density at high rates. The cells using such composite separator displayed better rate capability (Fig. 3C) and enhanced cycling stability (Fig. 3D) when compared with the cell using commercialized PP separator under the same conditions. This attractive result owned to its superior interfacial stability and high ionic conductivity of cellulose/PVDF-HFP composite separator [54]. ------Fig. 3-----13

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Polysulfonamide (PSA) is one kind of high performance synthetic polymers known for its excellent thermal, mechanical, dielectric properties and chemical resistance. To improve overall performance of cellulosed-based separator, Cui et al. fabricated cellulose/PSA composite membrane from mixture of microfibrillar cellulose and PSA via a facile papermaking process (Fig. 4A). LiFePO4/lithium cell employing

(Fig. 4B), indicting a superior thermal dimensional stability [55].

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------Fig. 4------

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cellulose/PSA separator exhibited perfect charge-discharge capability even at 120 °C

Very recently, Cui et al. successfully explored a sustainable, heat-resistant and

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flame-retardant cellulose-based composite nonwoven (FCCN) separator for LIBs [56]. This FCCN, which presented distributed pores with diameters ranging from 100 nm to

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200 nm, was made from cellulose pulp, sodium alginate, flame retardant and silica by papermaking approach. It was demonstrated that this FCCN separator possessed

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superior heat tolerance (Fig. 5A), excellent flame retardancy (Fig. 5B) and satisfactory mechanical strength. Owing to the facile ion transport and excellent interfacial compatibility of FCCN, the LiCoO2/graphite cell using FCCN separator

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exhibited better rate capability (Fig. 5C) and cycling retention than that using PP

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separator. Furthermore, the LiFePO4/Li cell with FCCN separator delivered a stable

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cycling performance and thermal dimensional stability even at 120 °C (Fig. 5D) [56]. ------Fig. 5------

Mitsubishi Paper Mills Ltd also reported many natural cellulose/synthetic polymer

fiber composite separators for LIBs [57-60]. Due to the good heat resistance of poly(ethylene terephthalate) (PET) fiber nonwoven and cellulosic materials, the cellulose/PET composite separator (NanoBase2) shows excellent heat resistance even at 220 °C, indicating a higher margin of safety. Meanwhile, the NanoBase2 composite shows improved mechanical strength and excellent protection against foreign particle because of the rich contents of ceramic particle. In addition to the inherent advantages of nonwoven kept after the ceramic coating, such as electrolyte wettability and ion conductivity, these composite separators displayed the longer cycle life than that of commercial polyolefin microporous membrane separators. Jim Schaeffer and Brian Morin, from Dreamweaver International (DWI), fabricated 14

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a high- performance separator for LIBs combinating of CNFs and cellulose microfibers. When the microfibers and nanofibers are combined, the cellulose composite material has the strength and openness of the microfiber scaffolding while the nanofibers drape over the microfibers strategically, closing down the pore size and maintaining a high permeability for ions. For safety testing including Nail penetration,

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over charge, short circuit, hot box and temperature cycling tests, this DWI separator of 30 microns in small 50 mAh pouch cells showed identical performance with that of

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trilayer PP/PE separators of 25 microns. Moreover, the DWI separator delivered a

film-base separators [61]. 3.6 Bio-inspired materials for battery separators

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higher energy at large discharge rates for all cell builds compared with several other

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In addition to the battery separators with biomass materials as the skeleton material, bio-inspired surface coating is another practical method to overcome the

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shortcomings of conventional PE separators. Messersmith et al. noticed the mussel’s strong adhesion ability onto virtually all types of surfaces and identified 3,4dihydroxy-L-phenylalanine and lysine peptides in Mytilus edulis foot protein 5 of

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mussel’s adhesive threads as the origins of the extraordinarily strong adhesion. Based

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on this interesting finding, they recognized that dopamine, a commercially available

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chemical, containing both catechol and amine groups, can function as a basis for the strong adhesion for various applications [62-64]. Inspired by the above-mentioned

works, Pyou et al. developed a simple dipping process to generate polydopaminecoated PE separators. After treatment, the color of PE separator changes to blackbrown, indicating the spontaneous deposition of thin polydopamine film on the surface of PE (Fig. 6 A, B). SEM images show that there is no obvious structure change after the polydopamine coating (Fig. 6C, D). Meanwhile, after the polydopamine coating, the surfaces of the separators transfer hydrophilic from hydrophobic and the wetting ability of electrolyte solvents on the separators is greatly improved. Taking advantage of the hydrophilic surface character, the modified PE separators exhibit significantly improved power performance without sacrificing the original advantages of PE separators (Fig. 6 E) [65]. Importantly, it was then demonstrated that lithium-metal anodes in LIBs with mussel-inspired polydopamine15

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coated separators exhibited excellent cycle life, which results from the suppression of Li-dendrite growth and the uniform Li ionic flux originating from the increased electrolyte uptake, as well as the strong mussel-inspired catecholic adhesion onto to the Li surfaces [66]. ------Fig. 6------

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In order to improve the mechanical strength of cellulose-based battery separator, especially in wet condition, Cui et al. explored the polydopamine treatment of

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cellulose membrane by a facile and low-cost papermaking process (Fig. 7A) [67]. It

was found that the composite membrane possessed compact porous structure, superior

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mechanical strength and excellent thermal dimensional stability. Compared with those of commercial PP separator and pristine cellulose separator, the cells using the

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composite separator displayed a superior rate capability (Fig. 7B) and excellent capacity retention (Fig. 7C). The bio-inspired polydopamine treatment has been

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demonstrated to be a versatile approach, and thus may be applicable to other separators with similar surface properties, to improve the surface property and mechanical strength.

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4. Biomass-derived binders

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------Fig. 7------

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As to LIBs, electrochemical capacitors and other energy storage devices, there have been extensive studies on electrode materials, separators, electrolytes and additives to achieve improvement of the device performance [68, 69]. Compared with the significant progress in these components, however, binders have not yet attracted extensive interests till now due to its characteristic of inactive material [70-72]. Typically, the binder provides structural integrity at relatively low mass fractions, bringing together the active material, the carbon black and the current collector. Although a binder is electrochemically inactive materials, considerable researching indicates that it can have a significant influence on the electrode performance especially for the newly-developed Si-based electrodes. In lithium batteries, a suitable binder must meet the following prerequisites [73]. (i) The binder is usually characteristic of polar groups such as -OH, (C=O)-OH, O(C=O)R, -SO3H, -CN or other groups in the side chain, delivering strong adhesion and 16

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high tensile strength at the interfaces between the active material powders, conductive carbon black powders and the current collector foils. (ii) The binder should stay physically and chemically stable after being immersed in the electrolyte, such as EC, propylene carbonate and dimethyl carbonate etc. (iii) The binder for cathode materials should possess wide electrochemical stability window up to 4.5 V (vs. Li+/Li)

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avoiding electrochemical oxidation when charged up to the cut-off voltage limit.

Similarly, the binder for the anode materials should have enough electrochemical

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reduction stability at low potential around 0 V (vs. Li+/Li). (iv) The binder cannot cause adverse effect on the impedance of the electron and Li+ diffusion for the

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electrode reaction. (v) The binder should be well dissolved or dispersed in the slurry and result in uniform distribution of both active materials and conductive carbon

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black. (vi) The binder and its utilization should be cost-effective, environmentalfriendly and safe.

M

------Fig. 8------

According to the interaction between the binders and the active powders, the binders can be divided into three types, i.e. dot-to-surface contact, segment-to-surface

contact

binders

comprise

te

to-surface

d

contact and network-to-surface contact, which are illustrated in Fig. 8 [73]. The dotof

the

emulsion

binders

such

as

Ac ce p

polytetrafluoroethene (PTFE) latex, styrene-butadiene-rubber (SBR) latex and polyacrylates latex. After mixing, coating and drying, these latex particles stick to the surface of the active particles and bind them together by point connection, which usually leads to weak adherence. The segment-to-surface contact binders include most of the polymer solution binders such as PVDF, carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyvinyl alcohol, polyacrylate and polyacrylonitrile solutions etc. After drying, the polymer chain segments adhere onto the surface of the active particles resulting in moderate adherence. The network-to-surface contact binders are characteristic of three-dimensional (3D) networks formed after coating via a thermal treatment or chemical reaction. Although 3D network causes strong adherence, the fabrication is complicated and the electrode sheets lack of flexibility. In regard to solvents, the binders can also be classified into two categories, organic solvent-based (nonaqueous) binders and water-based (aqueous) binders [74]. The non17

Page 17 of 66

aqueous binders are relatively expensive and harmful to environment because of using a large amount of organic solvent. In regard to environmental benignity and costeffectiveness, the aqueous binders have been attracted increasing attention [75, 76]. Among all the synthetic binders originating from the fossil oil, PVDF (as shown in Fig. 9) possesses superior electrochemical stability and are commercially used as

ip t

binder for LIB electrode fabrication [77-79]. However, there are still some drawbacks,

which limit the extensive application of PVDF. Firstly, PVDF is high-priced due to

cr

complicated synthesis and expensive monomer. Secondly, the expensive and volatile

N-methyl-2-pyrrolidone has to be used as solvent to dissolve PVDF, which further

us

raise the cost of the battery and pollute the environment as well. Thirdly, PVDF solution is seriously sensitive to moisture in air which can deteriorate its viscosity.

an

Finally, PVDF reacts with the lithium metal at elevated temperature which impairs the battery safety. Therefore, the development of greener, cheaper, and higher

M

performance binders is of great importance today for battery technology. ------Fig. 9-----The state-of-the-art LIBs composed of a transitional metal oxide cathode and a

d

carbon-based anode can only deliver an energy density around 150 W h kg −1, which is

te

far away from the requirement of EV for driving a distance of 200 km upon a single refuel. In order to meet the demand of 200 km, the higher energy density rechargeable

Ac ce p

batteries (300Wh kg −1) are desirable and the silicon-based anode batteries and lithium

sulfur (Li-S) batteries are expected to boost energy density even up to 300–500 W h kg−1. However, the cycle lives of Si electrodes are very short due to their significant volume expansion by up to 400% upon full lithiation and the sulfur cathode also suffers serious sulfur dissolution problem. Some natural polymers or their derivatives, such as CMC, alginate, amylopectin, carbonyl-β-cyclodextrin (C-β-CD) and gelatin have been recently explored to serve as robust and green binders to overcome the above mentioned defects of PVDF or huge volume expansion of the Si-based material or sulfur dissolution etc. The chemical structures of some typical biomass-derived binders are presented in Fig. 9, and the comparisons between the biomass-derived binders and PVDF are summarized in Table 4. The cells using these green binders typically exhibit high energy density, long cycle life, low cost, high safety, and 18

Page 18 of 66

environmental benignity compared to the conventional PVDF binder. ------Table 4-----4.1 Carboxymethyl cellulose-derived binder CMC is a cellulose derivative, and its backbone is made up by the coupling of carboxymethyl groups (-CH2-COOH) to some of the hydroxyl groups of the

ip t

glucopyranose monomers. It is nontoxic, and is generally considered to be

hypoallergenic. CMC membranes possess a good stiffness and a small elongation at

cr

break (5-8%). Its sodium salt, CMC-Na is well water-soluble and used as a viscosity modifier or thickener to stabilize emulsions in various products. CMC-Na serves

us

widely as the anode binders with lower fractions (usually 2~5 wt %). However, CMCNa molecules lack enough elasticity and always blend with elastic SBR to improve

an

the flexibility of the electrode sheets in LIBs [80-84].

The Si or Sn based anodes suffer from poor cycling stability owing to huge volume

M

changes during charge/discharge when using flexible PVDF as a binder. Owing to its stiffness nature, CMC-Na was proved to be an excellent binder for improving cycling stability of Si or Sn based anodes [85, 86]. It was further demonstrated that a self-

d

healing process of the strong Si-CMC hydrogen bonding is critical for superior

te

performances during cycling. This understanding leads to the well designing of Si-

Ac ce p

based electrodes with capacity retention reaching 1000 mAh g-1 of composite (i.e., full Si capacity) for at least 100 cycles and with a Coulombic efficiency close to 99.9% per cycle [87].

In order to improve CMC-Na binding performance, a noticeable work has been

done by Choi et al. They presented a thermally cured interconnected network of PAA and CMC-Na as a novel binder for silicon-based electrodes with superior performance even at high temperature [88]. The cross-linked PAA-CMC binder present excellent mechanical resistance to strain and even permanent deformation because of the 3D linked polymer chains. The adoption of cross-linked PAA-CMC binder can effectively mitigate the large volume expansion of silicon anodes upon lithium insertion compared to PVDF binder: the cross-linked PAA-CMC binder better accommodates the expansional strain of silicon and a volume expansion of 35% in the fully lithiated state can be obtained (Fig. 10A), whereas the use of the PVDF binder lead to a 19

Page 19 of 66

drastically increased volume expansion of about 130% (Fig. 10B). Nanosized silicon powder with a 3D network as binder exhibits a high reversible capacity of capacity of 1600 mAh g-1 for a very high current density of 30 A g-1 at 60 °C, which was much higher than those using the CMC-Na binder. ------Fig. 10------

ip t

To date, only very limited investigations of the effects of CMC-Na on cathode

materials have been carried out in comparison with different binders. As Passerini

cr

recently reported that CMC-based LiFePO4 electrodes dried at 170 °C were also able

to display a capacity cycling retention of 75% for 1000 cycles [89], which

us

corresponded to an overall capacity fading of only 0.025% per cycle. This is a support that CMC-Na might be electrochemically stable at positive potential over 3.6V (vs.

an

Li+/Li). It was also reported that the LiNi1/3Mn1/3Co1/3O2 electrode blended with CMC binder presented better cycling performance and rate capability than those with

M

alginate and PVDF binders. Electrochemical impedance spectroscopy results indicated that the LiNi1/3Mn1/3Co1/3O2 electrode using CMC as binder had much lower charge transfer resistance and lower activation energy than the electrodes using

d

alginate and PVDF as the binders [90, 91]. Moreover, Li et al studied the effects of

te

the SBR/CMC blending ratio on the dispersion and the electrochemical properties of

Ac ce p

LiCoO2 electrodes. It was demonstrated that CMC-Na was highly efficient in dispersing LiCoO2, and SBR contributed to uniform dispersion of the CMC-Na binder

and the flexibility of the electrode sheets after drying. This study revealed that the binder distribution had a significant influence on the electrical and electrochemical properties of the aqueous LiCoO2 electrodes than the dispersion of cathode powders did [92]. On the basis of the above-mentioned reports, it can be drawn a conclusion that the introduction of CMC-Na binder for cathode appears to be a very viable and promising solution to improve the overall electrode performance in a greener process. 4.2 Alginate-derived binder Alginate contains a specific carboxylic group in each of the homopolymer’s monomeric units (Fig. 9), which endows it a promising binder candidate especially for Si based anode. Recently, Yushin and his colleagues explored an alginate binder-based strategy to build Si anodes with improved performance characteristics for LIBs [93]. 20

Page 20 of 66

Compared with PVDF, the alginate binder, whatever in dry state or electrolyte solvent-impregnated wet state, shows much better mechanical properties. Importantly, when immersed into the electrolyte solvent, the stiffness of PVDF decays severely, whereas the stiffness of alginate does not change apparently (Fig. 11A-D). This strong stiffness of alginate is supposed to be of great benefit to the Si anode by alleviating

ip t

the large changes in particle volume. Although CMC has a similar mechanical property with alginate (Fig. 11A, B, and E, F), there is a natural and much uniform

cr

distribution of carboxylic groups along the chain of alginate but not CMC, which is responsible for the better transport of Li+ in the vicinity of Si nanopowders via

us

hopping of Li+ between the adjacent carboxylic cites, and the formation of a uniform and stable SEI layer on the Si surface, preventing degradation. Owing to the critical

an

properties of alginate, the mixing Si nanopowder with alginate yields a stable battery anode possessing a reversible capacity of 1200 mAh g-1 for more than 1300 cycles

M

(Fig. 12A), which was eight times higher than that of graphitic anodes. The reversible capacity of the cell for 100th cycles was also much higher than those using the PVDF and CMC binders (Fig. 12B) [93].

d

------Fig. 11------

te

------Fig. 12------

Ac ce p

The investigations of mussel-inspired adhesive materials have revealed that the catechol group plays a decisive role in the exceptional wetness-resistant adhesion [62, 94-97], which could be also very useful for improving binders’ properties in battery

because of the contact mode of each battery components in organic solvents. In 2013, Park et al. synthesized the catechol-conjugated alginate (3.4% ± 0.4% substitution) (Fig. 9) and discovered that the interaction between the Si and catechol-conjugated alginate is double than that without catechol conjugation on a single-molecule level via atomic force microscopy pulling tests (Fig. 13A). The Si electrodes with catecholconjugated alginate have good electrochemical stability and structural integrity, the enhanced film adhesion between Si and catechol-conjugated alginate can significantly improve the capacities and cycle performance of Si-based anodes (Fig. 13B). More importantly, since the wetness-resistant catecholic adhesion works availably with various substrates, this mussel-inspired catechol-conjugated alginate binder have 21

Page 21 of 66

potential applications in other LIB electrodes that suffer similar volume changes as Si during cycling [98]. ------Fig. 13-----4.3 β-cyclodextrin-derived binder β–CD is a 7-membered sugar ring molecule incorporating D(+)-glucose monomeric

ip t

units linked by α(1→4) linkages, and it can be easily obtained from ordinary starch by the well-established enzymatic hydrolysis method. The limited water solubility (1.85

cr

g in 100 g H2O at 25 °C) of β–CD restricts its application as aqueous binder in batteries; however via simple chemical modification or polymerization one can realize

[99, 100].

an

------Fig. 14------

us

the potential application of β–CD derivatives as binders in rechargeable Li batteries

By the partial carbonylation of hydroxyl groups of β–CD with H2O2, Wang and his

M

colleagues synthesized C-β–CD, which has a much better water solubility than β–CD and exhibits a strong bonding capability and electrochemical stability. When C-β–CD was utilized as a binder for sulfur-based cathodes, the high solubility and strong

d

bonding make C-β-CD forms a mechanically strong gel film around the surface of the

te

sulfur composite, which can effectively suppress the aggregation of the sulfur

Ac ce p

composite and reduce the dissolution of soluble polysulfide. As a result, satisfied electrochemical performances, including a high reversible capacity of 694.2 mAh g

(composite)

−1

and 1542.7 mAh g (sulfur) −1, a high sulfur utilization (92.2%) and a much

improved cycle performance (Fig. 14A), were achieved for the sulfur-based composite using C-β-CD as the binder [99]. Very recently, Choi and his colleagues reported a polymerized β–CD (β–CDp) as an effective multidimensional binder for Si

nanoparticle anodes in lithium batteries to mitigate the severe capacity fading caused by unparalleled volume change of Si during cycling [100]. In this work, hyperbranched β–CDp network structure, which incorporated a series of hydroxyl and

ether groups, was obtained from the reaction between β-CD and epichlorohydrin under strong basic conditions. Compared against other conventional linear binders, multidimensional noncovalent contacts between β–CDp and Si particles come into being, which can provide superior mechanical strength against the volume expansion 22

Page 22 of 66

of Si and also create a self-healing effect. Owing to the above advantages, β-CDpbased Si electrode presents significantly improved cycle performance (Fig. 14B), and the cycle performance can be further improved by the β-CDp/alginate hybrid binder in a synergistic effect [100]. Considering its low cost, environmental benignity and easy manipulation of modification (or polymerization), β-CD becomes a very attractive

ip t

binder candidate for practical adoption in rechargeable lithium battery manufacturing processes.

cr

4.4 Amylopectin-derived binder

Amylopectin, one of the most common polysaccharides, is a major component of

us

starch produced by plants. As a branched polymer of glucose, the linear chains of amylopectin are linked with α(1→4) glycosidic bonds, and branching occur every 24

an

to 30 glucose units with α(1→6) glycosidic linkages (Fig. 9). Recently, Komaba et al explored amylopectin as binder for Si-based electrodes, which exhibited significantly

M

higher capacity and better cycle performance (the capacity remains at ~800 mAhg-1 over 150 cycles,) in LIBs compared with PVDF binder. The improved performance of amylopectin binder is probably related to the degree of branching [101]. However, the

d

inferior adhesion ability resulting from the hydroxyl groups and the relatively higher

te

price of amylopectin might hamper its extensive application as a sustainable binder.

Ac ce p

4.5 Gelatin-derived binder

Gelatin is a translucent, colorless and flavorless solid substance, produced by

partial hydrolysis of collagen obtained from various animal by-products, and is usually classified as a foodstuff. As a mixture of peptides and proteins, gelatin possesses a plenty of amino and carboxyl groups, which might entail superior binder properties, e.g. good adhesion and fast ion diffusion. It was reported by Gaberšček et

al. that, gelatin has been successfully applied as a green binder for the graphite anodes [102, 103] and LiMn2O4 cathodes [104, 105]. The gelatin binder could mitigate the irreversible initial capacity loss of graphite anode because it could contribute to SEI formation. The gelatin binder could also be beneficial for the uniform distribution of conductive carbon black particles and improved the capacity and cycling stability of LiMn2O4 cathode. Gelatin was also successfully used as a new binder of the sulfur

cathode in lithium–sulfur batteries [106]. For the sulfur cathode, it is demonstrated 23

Page 23 of 66

that gelatin not only functions as an effective adhesive agent and dispersion agent, but also enhances the redox reversibility by slowing down the reducing reaction of elemental sulfur during the discharging process and reforming S8 after the charging process [107]. The drawback of the gelatin binder is lower electrochemical stability originating from the complicated chemical constituents and chemically instable

ip t

groups in gelatin, which hampers its real application in lithium batteries. 5. Biomass-derived electrode materials

cr

Current electrochemical energy devices mainly depend on the substantive use of

electrode materials that are far from renewable and sustainable, e.g. inorganic

us

compounds, which often require rare metals [4-7]. To merit the requirements of a resource-conserving, environment-friendly society, it remains great challenges and

intrinsic

properties

and

advantages,

an

significances to pursuit renewable and sustainable electrode materials. Owing to their including

the

environment-friendly

M

characteristics, the diverse structures, the intrinsic mechanical strength and flexibility, as well as the capability to efficiently accommodate other functional materials or liquid electrolyte, the renewable biomass and their derivatives have been

d

spontaneously considered as the possible alternatives to replace the traditional non-

te

sustainable electrode materials. In the past decade, some significant efforts have been

Ac ce p

put into developing sustainable and high-performance biomass-derived electrode materials: 1) The most broad research avenue is to apply biomass-derived nanostructures as renewable and favorable electrode materials in the advanced energy storage devices [13-15]. In order to be applied as electrode material, various electrochemically functional materials (e.g. conductive polymers, advanced carbon nanomaterials, etc.) have been integrated to endow cellulose composite with good electrical conductivity and electrochemical function. These conducting materials can be introduced into hierarchical biomass at different scales, from chemical modification of a biomass polymer at molecular scale to composite formation at nanofibrillated/microfibrillated fiber scale to surface coating onto biomass-based paper. 2) The other interesting and challenging research avenue is to facilely synthesize electroactive molecules from renewable natural biomass precursors via modern green chemistry concepts and then apply them as sustainable electrode 24

Page 24 of 66

materials [1]. In this section, we will present recent progress in the development of biomass derived electrode materials and their applications in energy storage. Although many works report the significant applications of pyrolyzed carbon, derived from diverse

of biomass, the related progress is not involved in this review.

ip t

biomass, as electrode materials [108-115], considering the subversive transformation

5.1 Conducting polymer/biomass composites as electrode materials polymers,

such

as

polypyrrole

(PPy),

polyaniline

(PANI),

cr

Conducting

polythiophene and poly(ethylenedioxythiophene), are organic polymers that are able

us

to conduct electrons and ions [116]. The characteristics of conducting polymers, including distinguished electrochemical and mechanical properties, low cost, ease of

an

processability, convenient modification of the chemical structures, and relatively light weight, allow them (typically PPy and PANI) to be used as attractive electrodes in

M

electrochemical capacitors and LIBs [117, 118]. However, conductive polymers suffer from low capacity since redox processes usually only occur at the surface of conducting polymer films due to limited accessibility. Thus, conducting polymers are

d

commonly deposited onto some substrates, in which the porous and less expensive

te

substrates are desirable [119-123]. Interestingly, the distinguished characteristics of

Ac ce p

biomass endow them as great candidates to modify the electrochemical and mechanical properties of the brittle conducting polymers. Biomass-conducting polymer composites can be molded in different shapes to obtain conductive paper material which can be either directly used as a working electrode or function as an underlying conductive substrate material for deposition of various metals or metal oxides [13, 124].

5.1.1 Polypyrrole (PPy)/biomass composites PPy, one typical conductive polymer, shows promise but too inefficient for practical

electrochemical energy storage applications, probably due to the inaccessibility and the thick and dense layers of the PPy material used [125]. Early in 1980s, the electrically conducting PPy/methylcellulose composite has been synthesized to improve the mechanical properties of PPy, which finally presented a maximum conductivity of 0.2 S cm-1 [126]. In recent years, despite extensive efforts to develop 25

Page 25 of 66

new cellulose-based electrodes for battery applications, there is no satisfactory charging performance to be obtained until in 2009 by one group at Uppsala University [127]. Strømme and colleagues firstly developed a novel nanostructured high-surface area electrode material of Cladophora nanocellulose coated with a 50 nm layer of PPy (Fig. 15A, B), which exhibited an exceptionally high ion-exchange capacity [128],

ip t

and then they explored the possibilities of utilizing these composite electrode

materials for energy storage in paper-based batteries (Fig. 15C, D) [127]. Cladophora

cr

algae cellulose has a unique nanostructure, entirely different from that of terrestrial

plants, and the possibility of energy-storage applications was raised in view of its

us

large surface area (80 m2 g−1). Batteries based on this prepared conductive paper composite material can be charged with currents up to 600 mA cm-2, with only a loss

an

of 6% after 100 charging cycles. The aqueous-based batteries entirely based on cellulose and PPy, also exhibit high charge capacities (between 25 and 33 mAh g−1). It

M

was demonstrated that the extreme thinness of the PPy layer coated on Cladophora algae cellulose played a critical role in obtaining a much higher charge capacity than the previous batteries based on advanced polymers.

d

------Fig. 15------

te

After their original work, Strømme and colleagues continued to complete some

Ac ce p

substantial works in this area. They reinforced the composites of PPy/Cladophora nanocellulose with 8 µm-thick chopped carbon filaments (Fig. 16). It suggests that the

nonelectroactive carbon filaments can decrease the contact resistances and the resistance of the reduced cellulose/PPy composite. The obtained paper-based energystorage devices by using the reinforced composites as electrode materials show enhanced capacitances and cycle performance (Table 5) [129]. Then, they detailedly investigated how different postsynthesis treatments (e.g. polymerization conditions, rinsing, and storage) affected both the short-term and the long-term properties (in terms of purity, chemical composition, conductivity, and electroactivity) of the Cladophora nanocellulose/PPy composite [130]. They also demonstrated that it was

possible to coat the individual fibers of wood-based nanocellulose with PPy using in situ chemical polymerization. The obtained dry composite exhibits an even better capacity performance than that of Cladophora nanocellulose/PPy composite (Table 5) 26

Page 26 of 66

[131]. ------Fig. 16-----In addition to Cladophora cellulose and land plant cellulose, other kinds of cellulose, e.g. bacterial cellulose and cotton cellulose [132, 133], can also be adopted to prepare high-performance cellulose/conducting polymer composites. The

ip t

core/sheath structured conductive nanocomposites were prepared by wrapping a

homogenous layer of PPy around bacterial CNFs (produced by Acetobacter xylinum)

cr

via in situ polymerization. By optimizing reaction protocols, the ordered core/sheath

bacterial CNFs/PPy nanostructure achieved an outstanding electrical conductivity as

us

high as 77 S cm-1, and demonstrated promising potential for supercapacitors, with a highest mass specific capacitance hitting 316 F g-1 at 0.2 A g-1 current density (Table

an

5) [132]. Porous nanocomposites consisting of cotton cellulose nanocrystals and PPy were fabricated using electrochemical co-deposition. The obtained nanocomposite

M

presented a high capacitance of 256 F g-1 and a good stability, which were comparable to that of a PPy/carbon nanotubes (CNTs) composite deposited under the same conditions [133]. Significantly, not only CNFs directly derived from natural

d

organisms have been used, some cellulose products, such as commercialized printing

te

paper, have also been demonstrated to be very suitable materials to fabricate

Ac ce p

biomass/conjugated polymer composite electrodes for electrochemical devices. Very recently, Zhou and colleagues reported a highly conductive paper fabricated through PPy coating on common printing paper, which shows a high electrical conductivity and good electrochemical performance as electrode material [134]. To further enhance the charge storage capacity of cellulose/PPy composites, the chemical doping seems an alternative approach. The PPy–cellulose composites doped with anthraquinone-2, 6-disulfonic acid via electropolymerization were prepared, which significantly increased the gravimetric charge capacity to 250 C g-1 due to the redox activities of PPy and the dopant [135]. ------Table 5-----Lignin is another abundant biomass in nature, and it has also been demonstrated to be efficient electrode material by forming lignin/conjugated polymer interpenetrating networks. Inspired by the fact that quinones usually play the role of soluble 27

Page 27 of 66

electron/proton transport agents in photosynthesis process and that lignin can be easily incorporated with large numbers of quinone sites from phenolic groups, Inganäs and colleagues created an inexpensive, electroactive conjugated polymer/biopolymer composite cathode by combining quinone electrochemistry and PPy conductivity [136]. The interpenetrating PPy/lignin composite film was electrochemically prepared

ip t

from a mixture of pyrrole and lignin derivatives from the brown liquor, which is a byproduct from the manufacture of paper pulp and is largely composed of

cr

lignosulfonate. The lignin-derived quinone group was used for electron and proton

storage and exchange during redox cycling, thus the charge storages of lignin and PPy

us

in the PPy/lignin composite were combined. It can be seen that in the galvanostatic discharge curves for the PPy/lignin composite films, two slopes are observed, which

an

should be ascribed to electrochemical activities of PPy and lignin-derived quinones respectively (Fig. 17). Especially for the thinner PPy/lignin composite film, it was a

M

favorable diffusion situation, and the capacities of lignin-derived quinones and PPy was calculated to be ~40 mAh g-1 and 30-35 mAh g-1, respectively (Fig. 17A). Finally, reasonable charge densities between 70 and 75 mAh g-1 were realized for the prepared

d

low-cost, green thin-film electrode [136].

te

------Fig. 17------

Ac ce p

5.1.2 (PANI)/biomass composites

As another outstanding conducting polymer, PANI has a relatively high theoretical

specific capacity (964 F g-1). However, PANI has common weaknesses with PPy, i.e. the limited achieved capacitance and the poor potential cycling stability [125, 137]. Recent studies showed that, the fabrication and application of highly porous PANIinorganic nanomaterial (CNTs, graphene, and metal oxides etc.) composites were very effective to improve the capacitance and stability by facilitating ion and solvent movements [125, 137-140]. Recently, biomass materials especially cellulose have also been explored as very promising scaffold materials for fabrication of PANI-based composites for energy storage applications [141-143]. Tang et al. prepared the bacterial CNFs-supported PANI nanocomposites with flake-shaped morphology via in situ polymerization of aniline onto bacterial CNFs scaffold, which presented a good electrical conductivity of 5.1 S cm-1, and a high mass-specific capacitance of 273 F g-1 28

Page 28 of 66

at 0.2 A g−1 in supercapacitor application [144]. Lei et al. prepared CMC/PANI nanorods with uniform diameters about 100 nm, and obtained a specific capacitance as high as 451.25 F g-1 and a good cycle performance [145]. Very recently, Deng et al. showed that the incorporation of Ag nanoparticles into CNF/PANI composite can provide fast electron transportation channels to achieve high capacitance. The solid-

ip t

state flexible supercapacitors based on the CNF/Ag/PANI aerogel can reach a high specific capacitance of 176 mF cm-2 at 10 mV s-1, and can remain the same

cr

electrochemical properties even under severe bending [141-143].

5. 2 Carbon nanomaterials/biomass composites as electrode materials

us

Carbon materials are always playing a critical role in energy conversion and storage [147]. Due to their novel size-/surface-dependent electronic, optical, mechanical and

an

thermal properties as well as catalytic properties, carbon nanomaterials, especially CNTs and graphenes, have been emerged as new class of electrode materials for the

M

next generation electrochemical energy storages. Tremendous efforts have been made to develop carbon-based high-performance energy storage devices, and many great progresses have been achieved [9, 148-150]. In the most recent development of and

versatile

energy

storage

d

flexible

devices,

various

types

of

carbon

te

nanomaterails/biomass composites have been explored as electrode materials, owing

Ac ce p

to the intrinsic characteristics of biomass materials. As systematically demonstrated, mesoporous cellulose fibers in these composite electrode not only functions as a substrate with large surface area but also acts as an interior electrolyte reservoir, where electrolyte can be absorbed much in the cellulose fibers and is ready to diffuse into an energy storage material [151]. 5. 2.1 Carbon nanotubes (CNTs)/biomass composites CNTs are the most common carbon nanomaterials selected to form composite

electrode with cellulose, due to their excellent properties, such as high conductivity, excellent electrochemical stability, low mass density, high mechanical strength, and high specific surface area. It is known that CNTs are particularly versatile in binding with cellulose. Recently, Ajayan and colleagues have developed a new nanocomposite paper energy storage technology which integrates the three basic components of an electrochemical storage device-electrode, separator and electrolyte-into single 29

Page 29 of 66

contiguous nanocomposite units that can serve as building blocks for thin, mechanically flexible electrochemical energy devices. Unmodified cellulose fibers were dissolved in a room-temperature ionic liquid (1-buty1,3-methylimidazolium chloride ([bmIm][Cl]), and then the cellulose solution was then coated onto vertically grown multi-walled CNTs (MWCNTs) to form the conductive nanocomposite paper,

ip t

in which MWCNTs were partially exposed from the cellulose-[bmIm][Cl] thin films (Fig. 18) [152]. This single contiguous nanocomposite paper can avoid the use of a

cr

separate electrolyte and spacer and is versatile to various supercapacitors and LIBs with electrolytes including aqueous solvents, room temperature ionic liquids, and

us

bioelectrolytes (Fig. 18). As a consequence, it was used as electrode for various flexible supercapacitor, battery, hybrid, and dual-storage battery-in-supercapacitor

an

devices, and the assembled devices displayed excellent electrochemical performance (Table 6). Recently, CNFs/MWCNT composites have also been successfully used as

M

electrode for constructing high-performance all-solid-state flexible supercapacitors (Table 6) [153, 154].

------Fig. 18------

d

It is worth noting that, in the most recent years, Cui, Hu and their colleagues have

te

paid much attention on the development of nanostructured, highly conductive

Ac ce p

cellulose paper for flexible energy and electronic devices [14, 19, 151, 155-160]. They demonstrated the generation of conductive electrodes on commercially available paper via forming conformal coating of single-walled carbon nanotubes (SWCNTs) or silver nanowire (AgNWs) films on the paper. The intrinsic properties of paper including high solvent absorption and strong binding with nanomaterials allow easy and scalable coating procedures by using simple solution processes (Fig. 19A, B). The prepared conductive paper has a sheet resistance as low as 1 Ω sq-1. Supercapacitors based on the CNT-conductive paper show excellent performance (on the basis of CNT mass): a specific capacitance of 200 F g-1 (Fig. 19C), a specific energy of 30–47 Wh kg-1, a specific power of 200 kW kg-1, and a stable cycling life over 40,000 cycles. This conductive paper has also been used as an excellent lightweight current collector in LIBs to replace the existing metallic counterparts (Fig. 19D). These results indicate that the performance of the prepared conductive paper is competitive with 30

Page 30 of 66

conventional metal foils and its related electrodes in which similar chemistries are used [155]. ------Fig. 19-----Cui, Hu and their colleagues carried out the first study on the optical properties of nanopaper substrates, and developed transparent and conductive composite materials

ip t

including tin-doped indium oxide, CNTs and AgNWs have been achieved on

nanopaper substrates, opening up wide applications in flexible optoelectronics and

cr

electrochemical devices [156]. They also reported a CNFs/CNTs/silicon-conductive

nanopaper for LIBs, the thin-layer of silicon was deposited on the CNFs/CNTs

us

substrate through a plasma-enhanced chemical vapor deposition method. Such lightweight and flexible Si-conductive nanopaper structure presents a stable capacity

an

of 1200 mAh g-1 for 100 cycles in half Li-ion cells [157].

Though its energy density is somewhat lower than that of LIB, sodium (Na)-ion

M

battery offers a fascinating alternative for low cost energy storage, because of the huge availability of sodium, its low price and the similarity of both Li and Na insertion chemistries [161]. Recently, Hu et al. demonstrated that the soft and

d

mesoporous wood fiber substrate can be utilized as an attractive platform for low cost

te

Na-ion battery electrode. A Sn thin film was deposited on a CNTs-precoating

Ac ce p

hierarchical wood fiber substrate, and the composite electrode thereby obtained was used as the anode for Na-ion battery, which can reach a stable cycling performance of 400 cycles with an initial capacity of 339 mAh g-1 at a current density of 84 mA g-1 (Fig. 20A). These exciting properties that come from the tnatural wood fiber-based Sn anode can simultaneously address the critical challenges associated with conventional Sn anodes. On the one hand, the soft nature of wood fibers can effectively accommodate the large volume expansion associated with the sodiation process (Fig. 20B). On the other hand, the hierarchical and mesoporous structure functions as an electrolyte reservoir that can enhance the ion transport kinetics (Fig. 20C) [19]. ------Fig. 20-----5.2.2 Graphenes/biomass composites The combination of CNTs with cellulose paper has shown promising application as 31

Page 31 of 66

electrodes of flexible energy storage devices. However, the selection and functionalization of diverse carbon nanomaterials remains optimization to further improve the performance of carbon-cellulose composites. Graphene, a twodimensional material consisting of a single layer of carbon atoms arranged in a honeycomb or chicken wire structure [162], has been extensively demonstrated as

ip t

another outstanding candidate. Cheng and colleagues developed a graphene–cellulose paper membrane material as a flexible electrode via a simple filtering method (Fig.

cr

21A). Via the strong electrostatic interaction, graphenes cover the cellulose fibers tightly (Fig. 21B), and are distributed through the macroporous texture of the filter

us

paper to form a conductive interwoven network. Due to the large capacitance (120 F g-1), low electrical resistance, and high strength, when the graphene-cellulose paper

an

electrode was used as freestanding and binder-free electrodes for flexible supercapacitors, satisfied performance was achieved (Fig. 21C, D) [163]. Various

M

graphene/cellulose composites, such as graphene/cellulose pulp composite, graphene sheets/cotton cloth composite, CNFs-reduced graphene oxide (RGO) hybrid aerogels, and CNFs-[RGO]n hybrid paper, have been recently fabricated via diverse process,

d

and all these composites shows excellent performances as the electrode materials of

te

supercapacitors (Table 6) [164-167].

Ac ce p

------Fig. 21------

------Table 6------

Most of the previously reported electronically conductive polymers or flexible

carbon nanomaterials-cellulose paper composite electrodes were fabricated by solution-based processes, which involve dispersing the active materials in a special solvent, followed by reforming the electrode on a substrate. The use of environmentally unfriendly chemicals and the requirements of post-treatment pose challenges for the wide applications of the techniques. More recently, Cui et al. developed a solvent-free approach to fabricate supercapacitor electrodes, i.e. by drawing with a graphite rod on standard printing paper. The supercapacitors thus fabricated show stable long cycling performance with 90% capacity retention after 15 000 cycles and a high areal capacitance of 2.3 mF cm-2. The drawing approach holds promising extension to fabricate other types of low cost energy storage device 32

Page 32 of 66

electrodes [159]. The above-mentioned composite electrodes typically derive high electronic conductivity from conducting materials (e. g. CNTs, graphene, conducting polymers), and fast ion transport from the hierarchical porosity of cellulose. Hu and colleagues clearly verified that mesopores within a cellulose fiber act as an electrolyte reservoir

ip t

and provide extra paths for ion transport. The use of porous, electrochemically inert cellulose paper as a substrate may sacrifice some volume energy and power density;

5.3 Biomass-derived small molecules as electrode materials

cr

however it provides efficient utilization of active storage materials at high rates [160].

us

Organic compounds offer new possibilities for high energy/power density, costeffective, environmentally friendly, and functional rechargeable lithium batteries. For

an

a long time, they have not constituted an important class of electrode materials, partly because of the large success and rapid development of inorganic intercalation

M

compounds. It is now becoming mandatory to develop renewable organic electrodes through eco-efficient processes and to decrease the consumption of non-renewable inorganic resources, the amount of waste produced as well as energy consumption.1 In

d

recent years, however, exciting progress has been made, bringing organic electrodes

te

to the attention of the energy storage community [168]. Especially, the biomass-

Ac ce p

derived organic materials have the potential to boost the capacity. Recently, the feasibility of using several active organic molecules that can be simply prepared from natural products common in living systems as electrode materials has been successfully developed by Tarascon and colleagues. ------Fig. 22------

Tarascon et al. firstly investigated the oxocarbon salt, Li2C6O6, as a candidate for

lithium-inserting positive electrodes. It can electrochemically react with Li+ by using carbonyl groups as redox centres, and can be synthesized from the natural organic sources through low-cost processes without using toxic solvents (Fig. 22). As compared with the few recent reports on carbonyl based organics, Li2C6O6, turned out to reversibly intercalate four extra lithiums per unit formula at an average voltage of 2.5 V, leading to energy densities and power-rate performances that compare to conventional cathodes with the advantage of being fully sustainable as it is made from 33

Page 33 of 66

the oxidation of the sugar inositol [169]. Consequently, Li4C6O6 [170], Li2C8H4O4 (Li terephthalate) [171], Li2C6H4O4 (Li trans–trans-muconate) [171] and lithium 2,6-bis (ethoxycarbonyl) -3,7-dioxo-3,7- dihydro-s-indacene- 1,5-bis(olate) [172] compounds were reported as key electrode materials for LIBs with attractive performances (Table 7). These molecules can also be readily prepared from biomass via eco-efficient

ip t

processes. However, to realize green, sustainable, fully-organic LIBs with comparable energy densities and power-rate performances and to completely understand the

cr

structure-function relationship of these small molecule compounds, further

------Table 7-----6. Conclusion and perspectives

us

investigations currently remains necessary.

an

Recent investigations have resulted in a significantly improved comprehension of the critical challenges for electrochemical energy storage systems. Biomass-based

M

materials have been demonstrated as very promising alternatives to conventional polyolefin separators, binder and substantial electrode materials in electrochemical energy storage devices and the recent processes have been emphasized in this review.

d

Owing to their sustainable, environmental friendly, cost-effective characteristics, the

te

application of biomass-based materials opens up new possibilities for the production

Ac ce p

of green, low-cost, up-scalable and lightweight energy storage systems, even fully recyclable paper-based batteries on a large industrial scale. Although the implementation of biomass-derived materials in green and sustainable

electrochemical energy storage systems holds great promise in a number of applications ranging from separators, binders to electrode materials, it is clear that considerable critical challenges still remain to be solved: 1) The principal challenge in the use of biomass-derived separators is the control of

thickness and porosity (particularly pore size and distribution, and thermal shutdown property). In addition, the hygroscopic nature, low mechanical strength and flammable property, are also the challenges need to be overcome for the development of biomass-derived separators for energy storage. 2) For the biomass-derived binders, some critical drawbacks have to be overcome such as variable quality, weaker adhesion on foils, stiffness at low temperature and 34

Page 34 of 66

high moisture uptake. Strict quality standards need to be issued to control the production quality and utilization, and the combination of biomass-derived binders with some other flexible binders can improve the dispersion and adhesion on foils and ameliorate the flexibility at low temperature. 3) The energy densities of biomass-derived energy devices are normally quite lower

ip t

than those of conventional metal-based systems. The critical issue in the use of

biomass-derived materials as electrode materials is the fact that they by themselves

cr

are electronically insulating and usually limited in functionalities, and thus the proper

integration with other conductive and functional materials is prerequisite and faces

us

many challenges. In addition, the stability, conformability and self-discharge of biomass-derived energy devices deserve intensive fundamental research.

an

Future research can emphasize the following key areas of development, which might favor the realization of more intriguing electrochemical energy storage devices

M

on the basis of biomass-derived materials:

1) Until now, most attention was paid to very numbered biomass materials, especially cellulose and its derivates. However, numerous other biomass materials

d

(e.g. lignin, marine polysaccharides, and biomass from agro-forestry wastes), with

te

their own specific structures and properties, also possess the potential applications as

Ac ce p

key materials for energy application, and thus merit intensive research devotion in the future. Additionally, large-scale production of biomass-derived materials with finely tuned structures and properties in even more low-cost and environmental friendly manners is critical for their applications in the energy storages. 2) It is obligatory to further improve their individual performance of biomass-

derived key materials for energy devices, even to endow them with additional functions by physical or chemical manipulation to biomass. For instance, by incorporating the biomass-derived separator with proper electro-active polymers, it is expected that the fabricated switchable separator can transform from an isolating state to a conducting state at a defined charging voltage to bypass the overcharging current and further improve the safety of the batteries. 3) It can be expected that the biomass-derived materials can also play promising

roles in the next-generation electrochemical energy devices, such as all-solid-state 35

Page 35 of 66

LIBs, Li-S batteries and Li-air batteries, with more significance and more challenges. The all-paper-device, in which all components are made by cellulose-derived materials, is also very promising and deserves intensive research efforts as a flexible, sustainable and high-performance energy device candidate. More importantly, the large-scale and low-cost fabrication of paper-based energy devices potentially can be

ip t

realized by using 3-D printing and other high-throughput nanofabrication techniques in the future [173].

cr

Acknowledgements

We thank Dr. Qingshan Kong, Dr. Chuanjian Zhang, Dr. Shanmu Dong, and Mr.

us

Jianjun Zhang for their fruitful discussions. This work was supported by the National High Technology Research and Development Program of China (863 program,

an

No.2013AA050905), the National Program on Key Basic Research Project of China (No. MOST2011CB935700), the Instrument Developing Project of the Chinese

M

Academy of Sciences (No. YZ201137), the Key Research Program of the Chinese Academy of Sciences (Grant No. KGZD-EW-202-2), National Natural Science Foundation of China (Nos. 21275151, 21271180 and 21344003), and Qingdao Key

Ac ce p

te

d

Lab of Solar Energy Utilization & Energy Storage Technology.

36

Page 36 of 66

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Hierarchical structure of wood fiber. [19], Copyright 2013. Reproduced

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Fig. 1.

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cr

interdigitated Li-ion microbattery architectures. Adv Mater 2013;25:4539-43.

with permission from the American Chemical Society. CNFs paper (CNP)-derived separators by Lee group: A) scanning electron

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Fig. 2.

microscopy (SEM) image of CNP separator. B) Comparison of liquid electrolyte (1 M LiPF6 in EC/DEC=1/1 v/v) immersion-height between the

d

PP/PE/PP separator and CNP separator. C) Comparison of cycling

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performance of cells assembled with PP/PE/PP separator or CNP separator.

Ac ce p

[48], Copyright 2012. Reproduced with permission from the Royal Society of Chemistry. D) SEM image of SiO2 decorated CNP (S-CNP) separator (SiO2=5wt.%). E) Comparison of liquid electrolyte (1 M LiPF6 in EC/DEC=1/1 v/v) immersion-height between the PP/PE/PP separator, CNP separator, and S-CNP separators (SiO2 = 1, 5, 10 wt.%). F) Comparison of

cycling performance of cells assembled with CNP separator, S-CNP separators, or PP/PE/PP separator. [52], Copyright 2013. Reproduced with permission from Elsevier Ltd.

Fig. 3.

Typical SEM image of the cellulose nonwoven (A) and cellulose/PVDFHFP composite nonwoven (B), and comparison of rate capability (C) and cycling performance (D) of LiCoO2/graphite cells assembled with PP separator and cellulose/PVDF-HFP composite separator. [54], Copyright 2013. Reproduced with permission from the American Chemical Society. 52

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Fig. 4.

A) Schematic of the preparation of cellulose/PSA composite membrane for LIB separator, and B) comparison of cycling performance of LiFePO4/Li cells assembled with PP separator and cellulose/PSA composite separator at 120 °C. [55], Copyright 2014. Reproduced with permission from the

Fig. 5.

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American Chemical Society. A) Thermal shrinkage behavior of FCCN and PP separators with increasing

the temperature, and the inset is the photograph of FCCN and PP separators

cr

after treating for 0.5 h at 150 °C. B) Combustion behavior of FCCN and PP

us

separators, showing the flame retardancy characterization of FCCN

separator. C) Comparison of rate capability of LiCoO2/graphite cells assembled with FCCN separator and PP separator. D) Comparison of

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cycling performance of LiFePO4/Li cells assembled with FCCN separator and PP separator at 120 °C. [56], Copyright 2014. Reproduced with

Fig. 6.

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permission from the Nature Publishing Group.

Preparation and application of the polydopamine-modified PE separator. A)

d

Photograph of PE separators immersed in dopamine solution without (left)

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and with (right) the buffer treatment at pH 8.5 after 24 h. B) Photograph of PE separators without (left) and with (right) the polydopamine

Ac ce p

modification. C) SEM image of PE separator and D) SEM image of PE separator with the polydopamine treatment, indicating that the polydopamine film is thin enough and does not modify the original morphology of PE separator. E) A comparison of discharging capacities between the pouch-type half-cell with polydopamine modified PE separator and the cell with PE separator. The measurements was performed between 3.0 and 4.5 V vs Li/Li+. [65], Copyright 2011. Reproduced with permission

from WILEY-VCH Verlag GmbH & Co. KGaA. Fig. 7.

A) Schematic illustration of the fabrication of cellulose/polydopamine (CPD) membrane, and the coating mechanism of polydopamine onto the surface of cellulose microfibers. B) Comparison of rate capability of LiCoO2/graphite cells assembled with CPD separator, cellulose separator, and PP separator. C) Comparison of cycling performance of 53

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LiCoO2/graphite cells assembled with CPD separator, cellulose separator, and PP separator. [67], Copyright 2014. Reproduced with permission from the Royal Society of Chemistry. Fig. 8.

Schematic illustration of the interactions between binders and active powders. A) dot-to-surface contact, B) segment-to-surface contact, and C)

Fig. 9.

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network-to-surface contact.

Chemical structures of PVDF and some biomass-derived binders.

cr

Fig. 10. Discharge-charge profiles of silicon composite electrodes with A) cross-

linked PAA-CMC binder (red line), and B) PVDF binder (blue line) at 175

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mA g-1 between 0.005 and 2.0 V versus Li/Li+. The black lines show the volume changes of electrodes during charging and discharging processes.

Verlag GmbH & Co. KGaA.

Atomic force microscopy indentation studies showing the Young's modulus

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Fig. 11.

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[88], Copyright 2012. Reproduced with permission from WILEY-VCH

comparison between the Na alginate (A, B), PVDF (C, D), and CMC (E, F) in both dry state and electrolyte solvent-impregnated wet state. [93],

d

Copyright 2011. Reproduced with permission from the American

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Association for the Advancement of Science.

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Fig. 12. A) Reversible Li-extraction capacity and Coulombic efficiency of the alginate binder-based nano-Si electrodes versus cycle number for Li insertion level fixed to 1200 mAh g-1 Si. B) Reversible Li-extraction

capacity of nano-Si electrodes with alginate, CMC, and PVDF binders versus cycle number at 4200 mA g-1 between 0.01 V and 1 V versus Li/Li+.

[93], Copyright 2011. Reproduced with permission from the American Association for the Advancement of Science.

Fig. 13. A) Atomic force microscopy force-distance curves and B) the cycling performance at a C/2 rate (2100 mA g−1) of the Si electrodes with catecholconjugated alginate (Alg-C), alginate (Alg), and PVDF binders, indicating that the better film adhesion caused by Alg-C leads to the better cycle performance. [98], Copyright 2013. Reproduced with permission from WILEY-VCH Verlag GmbH & Co. KGaA. 54

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Fig. 14. A) Cycle performance of sulfur-based cathodes with β-CD, C-β-CD, PVDF, and PTFE binders at 0.2 C. [99], Copyright 2013. Reproduced with permission from WILEY-VCH Verlag GmbH & Co. KGaA. B) Cycle performance of Si-based cathodes with β-CDp, alginate, and PVDF binders at 1C (4200 mA g−1). [100], Copyright 2014. Reproduced with permission

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from the American Chemical Society.

Fig. 15. SEM (A) and TEM (B) images of the PPy/Cladophora cellulose composite

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fiber. Schematic (C) and photograph (D) of the PPy/Cladophora cellulose composite paper-based battery cell. [127], Copyright 2009. Reproduced

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with permission from the American Chemical Society.

Fig. 16. Photograph (A) and SEM images (B, C) of PPy/Cladophora cellulose

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composite sample reinforced with 8 µm-thick chopped carbon filaments. [129], Copyright 2012. Reproduced with permission from WILEY-VCH

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Verlag GmbH & Co. KGaA.

Fig. 17. Discharge curves under galvanostatic conditions in 0.1M HClO4 for A) thinner (0.5 µm) and B) thicker (1.9 µm) PPy/lignin composite film, and the

d

linear regression lines used for capacitance analysis. [136], Copyright 2012

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The. Reproduced with permission from the American Association for the

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Advancement of Science.

Fig. 18. Fabrication and application of the cellulose fibers/[bmIm][Cl]/vertically grown CNTs conductive nanocomposite paper units. A) Schematic of the supercapacitor and LIB assembled by using nanocomposite paper units. B) Photographs of the nanocomposite units demonstrating flexible property. C) SEM image and corresponding schematic of the nanocomposite paper showing MWNTs protruding from the cellulose–[bmIm][Cl] thin films. [152], Copyright 2007. Reproduced with permission from the National Academy of Sciences. Fig. 19. A) Conformal coating of CNT or Ag NW ink on commercial Xerox paper via Meyer rod method. B) The photograph of conductive Xerox paper after CNT coating. C) Gravimetric capacitances of CNTs-conductive paper at various currents measured in aqueous and organic electrolytes, and data 55

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from CNTs on PET are presented for comparison. D) Cycling performance of LiMn2O4 nanorod and Li4Ti5O12 nanopowder half LIBs with CNTsconductive paper as the current collectors. [155], Copyright 2009. Reproduced with permission from the National Academy of Sciences. Fig. 20. A) Discharge–charge profiles of the Na-ion battery based on the anode of

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50 nm Sn on CNTs-precoating wood fiber (Sn@WF) at a rate of C/10. B) Schematic of how the soft wood fibers release the sodiation generated

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stresses experienced by the Sn@WF electrode. C) Schematic of the dual pathways for Na+ transport that effectively enhance the kinetics of the

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Sn@WF anodes for Na-ion batteries. [19], Copyright 2013. Reproduced with permission from the American Chemical Society.

an

Fig. 21. A) Schematic of the fabrication process of the graphene–cellulose paper membrane material. B) Typical SEM image of the graphene–cellulose paper

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electrode, indicating the anchor of graphenes on the cellulose fiber surface. C) Cyclic voltammetry (CV) curves of the graphene–cellulose paper electrode in 1 M H2SO4, showing an excellent capacitive behavior. D)

d

Cyclic performance of the graphene–cellulose paper electrode measured at

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50 mV s-1. Inset: CV curves of the 1st and the 5000th cycle. [163], Copyright

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2011. Reproduced with permission from WILEY-VCH Verlag GmbH & Co. KGaA.

Fig. 22. The proposed sustainable organic-based LIBs on the basis of biomassderived electrode materials. Electrochemically active Li2C6O6 can be prepared from corn-extracted myo-inositol, whereas electrochemically active polyquinone can be polymerized from apples-extracted malic acid (center). [1], Copyright 2008. Reproduced with permission from the Nature Publishing Group.

Table 1 The basic information of several typical biomass materials

56

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Biomass Cellulose

Structures

Extract from plants; Fibrillation and refining of cellulose pulp; Bacterial synthesis Extract from seaweeds

Properties Abundant, high dielectric constant, heat resistance, and good chemical stability Hydrophilic, highly viscous, odorless and tasteless, and good stability

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te

d

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an

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cr

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Alginate

Manufacture methods

57

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Table 2 General parameters for LIB separators. Reproduced with permission from Ref. [24], Copyright 2004 American Chemical Society.

Sale price ($ m-2)

< 1.00

Thickness (um) Permeability (MacMullin, dimensionless)

< 25

Test Method (N.A. = not available) the American Society for Testing and Materials (ASTM) Test Method D5947-96

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Goal

cr

Parameter

Complete wet out in typical battery electrolytes Stable in battery for 10 year

Wettability

N.A. N.A.

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Chemical stability

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< 11

Pore size (um)

<1

Puncture strength

> 300 g/25.4 um < 5% shrinkage after 60 min at 90 °C < 50 ppm H2O

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Thermal stability Purity Tensile strength (for spirally wound)

ASTM D1204

ASTM Test Method D882-00

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te

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< 2% offset at 100psi

ASTM Test Method E128-99 ASTM F1306-90

58

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cr

i Thickness (um)

Cellulose/PVDF-HFP

27

40

PET/Cellulose, FPC 2515 (Nanobase2, Mitsubishi Paper Mills) PET/Cellulose, FPC 3018 (Nanobase2, Mitsubishi Paper Mills) Micro-/Nanocomposite cellulose material (DWI)

23

60

Ac

30

30

Pore size (um) 0.7

66

~0.3

ed

cellulose-based composite nonwoven (FCCN)

Porosit y (%) 65

0.3

4.7

0.6

45

70

pt

40

53

7.0

59

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Cellulose/Polysulfona mide

Gurley (s/100cc ) 36

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Property

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Table 3 Principal features of cellulose-based composite separators.

110

55

0.5

0.5

TD shrinkage (%) 0 (at 200 °C)

MD shrinkage (%) 0 (at 200 °C)

TD strength (MPa) -

0 (at 200 °C)

0 (at 200 °C)

0 (at 200 °C)

0 (at 200 °C)

< 0.3 (at 180 °C)

< 0.3 (at 180 °C)

353

< 0.3 (at 180 °C)

< 0.3 (at 180 °C)

490

0 (at 90 °C) 0 (at 160 °C)

0 (at 90 °C) 2 (at 160 °C)

90

160

50

MD strength (MPa) -

Elongation (%)

160

50

490

700

180

3

6

5

3

3

4

Fabricati ng method Electrospi n & coating Paper making

Paper making

Paper making

Remarks Good interfacial stability Good flame retardancy and thermal stability Heatresistant and flameretardant High strength and heat resistance

Paper making

High strength

Paper making

Even currents

[54]

[55]

[56]

[60]

[60]

[61]

59

Page 59 of 66

Ref

i cr

Advantages

cathode materials such as LiFePO4, LiCoO2, LiMn2O4, LiNi(1/3)Co(1/3)Mn(1/3)O2, etc.

chemical synthesis; superior electrochemical stability;

expensive; using organic solvent; sensitive to moisture; high ionic impedance

chemical synthesis; cheap; excellent elasticity; environmental-friendly

graphite anode

CMC-Na

graphite anode; Si, Sn or Ge based anodes; LiFePO4 Cathode

ce

pt

SBR

Si, Sn or Ge based anodes

Ac

Alginate-Na

M

PVDF

Cost $/kg

Applicable scope

Disadvantages

Ref

20~30

[77-79]

poor chemical stability; low electrochemical stability;

3~5

[80-84]

carboxylmethylation from cellulose; cheap; environmental-friendly; high viscous and less dosage; low ionic impedance; stiffness (good to Si based anode)

stiff and poor flexibility; variable chemical structure; variable slurry viscosity

2~5

[85-91]

extracted from aquatic brown algae; moderate price; carboxyl group evenly distribution; lower ionic impedance; high stiffness in electrolyte;

variable M and G-blocks; variable slurry viscosity;

10~14

[93]

ed

Binders

an

us

Table 4 The comparison of PVDF and biomass-derived binders.

Alginate (catecholconjugated)

Si based anodes

catechol conjugated alginate; strong adherence; wetness-resistant adhesion

complicated synthesis; low substitution

>10

[98]

β-CD

sulfur based cathode, Si based anodes

produced from starch by means of enzymatic conversion; cheap; environmental-friendly

low viscosity

3~4

[99, 100]

60

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i cr us

Si, Sn and Ge based anodes

Gelatin

graphite anode, LiMn2O4 cathode, sulfur based cathode

obtained from various animal by-products; moderate price; SEI improvement

easy to degrade; variable molecular weight; variable slurry viscosity; moderate adherence electrochemical instability; complicated constituents; pH-dependent viscosity

5~7

[101]

7~10

[103-107]

Ac

ce

pt

ed

M

an

Amylopectin

obtained from starch; cheap; environmental-friendly

61

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i cr us

an

Table 5 Literature data on biomass/conducting polymer composites-based electrodes for supercapacitor or battery applications.

Conductivity (S cm-1)

nanocellulose/PPy conductive paper composite nanocellulose/PPy/carbo n filaments conducting composite

in situ chemical polymerization

Remarks

Ref.

PPy layer (50 nm in thickness) was coated on Cladophora algae cellulose

[127]

8 µm-thick chopped carbon filament was used to strength the nanocellulose/PPy composite

[129]

~ 1.5 S cm-1

77 mAh g−1 ~60–70 F g−1 1.75 Wh kg−1 2.7 kW kg−1 80 mAh g-1

Wood-based nanocellulose was used

[131]

77 S cm-1

316 F g-1 at 0.2 A g-1

Bacterial cellulose produced by Acetobacter xylinum was used

[132]

/

256 F g-1

Cotton extracted cellulose nanocrystals were used

[133]

Common printing paper was used

[134]

PPy was doped with anthraquinone- 2,6-disulfonic acid

[135]

Lignin derivatives from the brown liquor (a byproduct from the manufacture of paper pulp) was used Bacterial CNFs was used

[136]

M

Preparation

> 1 S cm-1

ed

Electrodes

pt

in situ chemical polymerization followed by acid-wased

Device Performance: Capacity (F g−1) or Capacitance (mAh g−1) or Energy Density (Wh kg− 1) or Power Density (kW kg− 1) 25 mAh g−1 at 10 mA 33 mAh g−1 at 320 mA

/

in situ chemical polymerization in situ chemical polymerization of selfassembled pyrrole

“soak and polymerization” method

15 S cm-1

cellulose/PPy composites

chemical polymerization followed by electropolymerization electrochemical polymerization of pyrrole in situ polymerization of

/

0.42 F cm-2 1 mWh cm-3 0.27 W cm-3 250 C g-1 (charge capacity)

~ 1 S cm-1

70-75 mAh g-1

5.1 S cm-1

273 F g-1 at 0.2 Ag−1

ce

nanocellulose/PPy conducting composite nanocellulose/PPy core/sheath structured conductive nanocomposite cellulose/PPy conductive nanocomposite printing paper/PPy composite

co-

Ac

electrochemical deposition

lignin/PPy interpenetrating networks CNFs/PANI

[144]

62

Page 62 of 66

i cr 451.25 F g-1

/

1Ω sq-1 (for CNF/Ag aerogel)

176 mF cm-2 at 10 mV s-1

Commercial CMC was used

[145]

Bleached kraft softwood pulp-derived CNFs was used

[146]

Ac

ce

pt

ed

M

CNFs/Ag/PANI aerogel

us

CMC/PANI nanorods

aniline onto bacterial CNFs via one-step in-situ oxidation polymerization electrodeposition of PANI onto Ag/CNFs

an

nanocomposites

63

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i cr

cellulose fibers/[bmIm][Cl]/ vertically grown CNTs conductive nanocomposite paper CNFs/MWCNT nanohybrid aerogel

Infiltrating cellulose/ ([bmIm][Cl]) solution into the MWNT film

/

supercritical CO2 drying.

/

ed

pt

buried-in method

the Meyer rod coating method

ce

microfibrillated cellulose /MWCNT composite SWCNTs or AgNWs /paper composite

M

Preparation

paper-making technique, manual Meyer rod coating, plasmaenhanced chemical vapor deposition method solution-based coating of CNTs, electrodeposition of MnO2 solution-based coating of CNTs, electrodeposition of Sn filtering a GNS suspension through a filter paper paper-making process

Ac

CNFs/CNTs/siliconconductive nanopaper

homemade cellulose paper/CNTs/MnO2/ CNTs natural wood fiber/CNTs/Sn film graphene–cellulose paper membrane material graphene/cellulose

Device Performance: Capacity (F g−1) or Capacitance (mAh g−1) or Energy Density (Wh kg− 1) or Power Density (kW kg− 1) 36 F g−1 (in KOH electrolyte) 22 F g−1 (in RTIL electrolyte) 13 Wh kg-1 1.5 kW kg-1 110 mAh g−1 at 10 mA g-1 178 F g-1 at 5 mV s-1 13.6 mW cm-2, 20 mWh cm-2,

an

Conductivit y

Electrodes

us

Table 6 Literature data on carbon nanomaterials/biomass composites-based electrodes for supercapacitor or battery applications.

8.2x10-4 cm-1 10 Ω sq-1

~80 Ω sq-1

10.7 Ω

~ 30 Ω sq-1

6 Ω cm 11.6 S m-1

S

154.5 mF cm-2 at 20 mV s-1 -1

200 F g , 30–47 Wh kg-1, 200,000 W kg-1 1200 mA h g-1 at 0.8 A g-1

Remarks

Ref.

The nanocomposite paper contains MWNTs as the working electrode and the cellulose surrounding individual MWNTs, as well as the extra layer as the spacer and the RTIL in cellulose as the self-sustaining electrolyte 1) All-solid-state flexible supercapacitors are fabricated using CNFs/MWCNTs film as electrode material and charge collector. 2) The device remains at 99.9% of the initial capacitance after 1000 cycles Flexible all solid-state supercapacitors were fabricated for tests 1) Capacitor owns a stable cycling life over 40,000 cycles. 2) Conductive paper can also been used as an excellent lightweight current collector in LIBs 1) The lightweight and flexible Si-conductive nanopaper structure performs as LIB anodes. 2) After 100 cycles, the discharge capacity still remains 77% compared to the first cycle.

[152]

[153]

[154]

[155]

[157]

327 F g-1 at 10 mV s-1 201 F g-1 at 200 mV s-1

The capacitance retention was reached with 96, 93, 88, and 85% at the 20000th, 30000th, 40000th, and 50000th cycles, respectively.

339 mAh g-1 at 84 mA g-1

Natural wood fiber/CNTs/Sn film composite electreode-based Na-ion batteries were developed. The supercapacitor retains > 99% capacitance over 5000 cycles.

[163]

The

[164]

120 F g-1 252 F g-1 at 1 A g-1,

flexible

and

mechanically

tough

[151]

[19]

64

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i cr

CNFs–[RGO]n paper

hybrid

LbL self-assembly approach

drawing with a graphite rod on standard printing paper

100 S m-1

2.4 kΩ m-1 (20 layers of RGO) 223 Ω cm-1

2.3 mF cm-2 at 200 mA g-1 12 F g-1

composite works well in both supercapacitors and LIBs. The supercapacitors fabricated using the GNSs–CC composite have good cycle durability in both 6 M KOH and 2 M EMIMBF4/acetonitrile electrolytes (6-7% decay of capacitance after 1500 cycles).

The device capacitance still retains about 99.1% of the initial capacity after 5000 charge-discharge cycles. After 5000 cycles, the capacitance decay is ~ 19%. The transmittances of T-SC-10 and T-SC-20 are about 56% and about 30% (at 550 nm) respectively. 1) Paper supercapacitors by a solvent-free drawing method were developed. 2) The supercapacitor has excellent cycling performance with nearly 100% retention of capacity up to 3000 cycles.

[165]

[166]

[167]

[159]

Ac

ce

pt

carbon nanomaterialscellulose paper composite

supercritical CO2 drying.

326.8 F g-1 at 10 mV s-1, 7.13Wh kg-1 in 6 M KOH electrolyte; 73.2 F g-1 at 0.1 A g-1, 12.3 Wh kg-1 in 2 M EMIMBF4/acetonitrile electrolyte 207 F g-1 at 5 mV s-1, 15.5 mW cm-2, 20 mW h cm-2 1.73 mF cm-2 at 5 mV s-1

an

hybrid

225 Ω cm-1

M

CNFs-RGO aerogels

brush-coating and drying

ed

graphene sheets/cotton cloth nanocomposite

us

257 mAh g−1 at 200 mA g-1

composite paper

65

Page 65 of 66

Table 7 Small molecules derived from biomass as electrode materials for LIBs.

Compound

Structure

E (V) vs Li+/Li0

Capacity (mAh g-1)

Remarks

Ref

2.5

580

contains carbonyl groups capable of reversibly reacting with four extra Li+ per formula

[169]

1.8

~200

contains carbonyl groups capable of reversibly reacting with two extra Li+ per formula

1.4

150

0.8

300

O

Dilithium rhodizonate salt (Li2C6O6)

LiO

O

LiO

O

ip t

O O

Tetralithium rhodizonate salt (Li4C6O6)

OLi

LiO

OLi

C H

H C

C H

H C

OL O

O

OLi

LiO

O

LiO

O

O

O

O

O O

OLi

~1.96 ~1.67

with carboxylate groups capable of reversibly reacting with one extra Li+ per formula with carboxylate groups capable of reversibly reacting with two extra Li+ per formula

125

with both carbonyls and ester redox centers capable of reversibly reacting with two extra Li+ per formula

[170]

[171]

[171]

[172]

M

Lithium 2,6-bis (ethoxycarbonyl)3,7-dioxo-3,7dihydro-s-indacene1,5-bis(olate)

LiO

us

Di-lithium terephthalate

O

cr

O

trans-

an

Di-lithium trans -muconate

LiO

Ac ce p

te

d

\

66

Page 66 of 66